US6346650B1 - Method for making mixed high purity (meth)acrylic anhydrides - Google Patents

Method for making mixed high purity (meth)acrylic anhydrides Download PDF

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Publication number
US6346650B1
US6346650B1 US09/601,240 US60124000A US6346650B1 US 6346650 B1 US6346650 B1 US 6346650B1 US 60124000 A US60124000 A US 60124000A US 6346650 B1 US6346650 B1 US 6346650B1
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meth
process according
acrylate
alkali metal
reaction
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US09/601,240
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English (en)
Inventor
Jean-Michel Paul
Alain Riondel
Frédéric Fabis
Sylvain Rault
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Arkema France SA
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Atofina SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates

Definitions

  • the present invention relates to a process for manufacturing mixed anhydrides represented by the general formula (I):
  • R 1 represents H or CH 3 ;
  • R 2 represents an alkyl, alkenyl, aryl, alkaryl or aralkyl residue, according to which process an alkali metal (meth)acrylate of general formula (II):
  • R 1 is as defined above;
  • M is an alkali metal, is reacted with a chloroformate of general formula (III):
  • R 2 is as defined above.
  • R 1 being as defined above. This is particularly inconvenient when it is desired to synthesize carboxyalkoxy (meth)acrylic anhydride containing very little methacrylic anhydride.
  • a subject of the present invention is thus a process for preparing a high-purity mixed (meth)acrylic anhydride (I), by reaction between the abovementioned compounds (II) and (III), characterized in that the said reaction is carried out in an aqueous medium and in the absence of amines, the chloroformate (III)/alkali metal (meth)acrylate (II) molar ratio being at least equal to 1.15.
  • R 2 is chosen from C 1 -C 40 alkyl, C 2 -C 40 alkenyl, phenyl, phenyl (C 1 -C 40 alkyl) and (C 1 -C 40 alkyl) phenyl residues;
  • M represents Na or K.
  • the mixed anhydrides of formula (I) in which R 2 represents C 1 -C 40 alkyl, such as ethyl, n-propyl, isopropyl, n-butyl or isobutyl, are of particular interest and constitute a family of preferred mixed anhydrides of the invention.
  • These are mild acylating agents which can very advantageously replace methacrylic anhydride or (meth)acryloyl chloride which generate methacrylic acid or hydrochloric acid in acylation reactions.
  • the chloroformate (III)/alkali metal (meth)acrylate (II) molar ratio can be between 1.15 and 2, preferably between 1.5 and 1.7, in order to limit the formation of by-products of the type
  • the reaction according to the present invention is advantageously carried out at a temperature of between ⁇ 10 and +30° C., preferably between +10 and +20° C.
  • the alkali metal (meth)acrylate (II) is prepared in aqueous solution by neutralizing (meth)acrylic acid with the hydroxide MOH, the MOH/(meth)acrylic acid molar ratio being between 1 and 1.5, in particular between 1 and 1.1, and the water/alkali metal (meth)acrylate (II) weight ratio being between 1.5 and 7, in particular between 1.5 and 2, after which the chloroformate (III) is reacted with the alkali metal (meth)acrylate (II).
  • the reaction between the alkali metal (meth)acrylate (II) and the chloroformate (III) is carried out in the presence of a phase-transfer catalyst, dissolved or fixed to a polymeric support such as a styrene-divinylbenzene copolymer or a crosslinked polyvinyl-pyridine resin and used in particular in a proportion of from 0.001 to 0.02 mol, in particular from 0.005 to 0.01 mol, per mole of alkali metal (meth)acrylate (II).
  • phase-transfer catalyst is advantageously chosen from quaternary ammonium salts, phosphonium salts and crown ethers.
  • R 4 to R 7 each represent C 1 -C 40 alkyl, such as CH 3 , C 2 H 5 , C 4 H 9 , C 8 H 17 and C 16 H 33 , or aryl such as phenyl, or aralkyl such as benzyl;
  • X represents one from among Cl, Br, I, OH and HSO 4 ;
  • tetramethylammonium chloride benzyltrimethylammonium chloride, benzyltri-n-butylammonium chloride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, methyltrioctylammonium bromide and tetra-n-butyl-ammonium hydrogen sulphate;
  • crown ethers mention on may be made of 18-crown-6 and dibenzoyl-18-crown-6.
  • the reaction according to the invention is generally carried out with stirring in a thermostatically-controlled jacketed reactor while rigorously controlling the temperature.
  • the crude reaction mixture separates out into two phases by settling if the stirring is stopped (or into three phases if a phase-transfer catalyst is used, fixed to a polymeric support).
  • the reaction progress is monitored by regularly taking samples of the aqueous phase and assaying the residual alkali metal (meth)acrylate (II).
  • the reaction is considered as complete when the degree of conversion of the alkali metal (meth)acrylate (II) is greater than 95%.
  • the phases of the two-phase or three-phase reaction mixture are separated by settling at room temperature, advantageously washed with water (amount: 20 to 100% of the weight of the organic phase, preferentially 30 to 40%) at room temperature, the organic phase containing the mixed anhydride (I) and the excess chloroformate (III) then being stripped off under vacuum at a temperature of less than or equal to 35° C.
  • the mixed anhydride is thus obtained in very high purity.
  • At least one polymerization inhibitor into the reaction medium, in a proportion of from 500 to 5000 ppm, in particular from 500 to 1000 ppm, relative to the alkali metal (meth)acrylate (II)—or to its precursor (meth)acrylic acid—in order to overstabilize the latter.
  • polymerization inhibitors examples include hydroquinone methyl ether, hydroquinone, phenothiazine and di-tert-butyl-para-cresol.
  • the heterogeneous mixture is stirred for 15 hours.
  • the phases are then separated by settling at room temperature.
  • the organic phase is dried over calcium sulphate and the volatiles are then stripped off under vacuum at a temperature of less than 35° C., in order to remove the excess chloroformate.
  • Example 1 is repeated, modifying the temperature and the ethyl chloroformate/sodium methacrylate molar ratio.
  • Example 2 3 4 5 Ethyl chloroformate/sodium 1.5 1.5 1.5 3 methacrylate molar ratio Temperature (° C.) 5 25 35 15 Reaction time (h) 30 8 7 24 Degree of conversion of the sodium 81 90.3 97.4 98.5 methacrylate (%) Composition of the organic phase separated out by settling (% by weight) ethyl chloroformate 39.7 29 22.5 63 carboethoxymethacrylic anhydride 55 63 65 35 methacrylic anhydride 5 7 11 2 ethanol ⁇ 1 ⁇ 1 1 water 0.3 0.2 0.1 Composition of the organic phase stripped of volatiles (% by weight) carboethoxymethacrylic anhydride 91 90 85.5 94.5 methacrylic anhydride 9 10 14.5 5.5
  • the reaction mixture is left stirring while controlling the temperature at 20° C.
  • the reaction progress is monitored by assaying the residual sodium methacrylate in the aqueous phase separated out by settling (the phases of the mixture separate out by settling as soon as the stirring is stopped). After reaction for 3 hours, the degree of conversion of the sodium methacrylate is greater than 99%.
  • the reactor is then emptied, the phases of the reaction mixture are separated by settling at room temperature, the organic phase is washed with 57 g of water and the washed organic phase is separated out by settling.
  • Example 6 is repeated, varying the ethyl chloroformate/sodium methacrylate molar ratio.
  • Example 3 The reaction progress is monitored as in Example 3. After reaction for 4 hours, the degree of conversion of the sodium methacrylate is greater than 99%. The phases of the crude product are then separated out by settling but not washed, and stripped of volatiles under vacuum at a temperature of less than 35° C.
  • the yield of carboethoxymethacrylic anhydride is 87.5%.
  • Example 6 is repeated, using potassium methacrylate instead of sodium methacrylate and working at 10° C.
  • composition of the final product (% by weight) is as follows:
  • Example 6 is repeated, working at 10° C. and varying the nature of the phase-transfer catalyst, which is introduced in an amount of 0.01 mol/mole of sodium methacrylate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US09/601,240 1998-02-02 1999-01-28 Method for making mixed high purity (meth)acrylic anhydrides Expired - Fee Related US6346650B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9801155 1998-02-02
FR9801155A FR2774375B1 (fr) 1998-02-02 1998-02-02 Procede perfectionne de fabrication d'anhydrides (meth)acryliques mixtes de haute purete
PCT/FR1999/000164 WO1999038837A1 (fr) 1998-02-02 1999-01-28 Procede perfectionne de fabrication d'anhydrides (meth)acryliques mixtes de haute purete

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US6346650B1 true US6346650B1 (en) 2002-02-12

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US (1) US6346650B1 (cs)
EP (1) EP1071650A1 (cs)
JP (1) JP3533178B2 (cs)
KR (1) KR20010040542A (cs)
CN (1) CN1135219C (cs)
AU (1) AU2167799A (cs)
CA (1) CA2319673C (cs)
CZ (1) CZ296363B6 (cs)
FR (1) FR2774375B1 (cs)
ID (1) ID26417A (cs)
WO (1) WO1999038837A1 (cs)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007101563A3 (de) * 2006-03-03 2007-10-25 Cognis Ip Man Gmbh Bei raumtemperatur flüssige verbindungen

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2799753B1 (fr) * 1999-10-19 2002-01-04 Atofina Procede perfectionne de fabrication d'anhydrides symetriques
JP2007039345A (ja) * 2005-08-01 2007-02-15 Sumitomo Chemical Co Ltd 混合酸無水物の製造方法
CN103588635A (zh) * 2013-10-11 2014-02-19 青岛文创科技有限公司 一种 2-甲基丙烯酸酐的制备方法
CN108191643A (zh) * 2018-01-18 2018-06-22 上海仁实医药科技有限公司 一种氯乙酸酐的合成工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3718675A (en) 1970-06-18 1973-02-27 Stevens & Co Inc J P Carbonic carboxylic anhydrides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1133727B (de) * 1960-11-08 1962-07-26 Bayer Ag Verfahren zur Herstellung gemischter Carbonsaeure-kohlensaeure-monoester-anhydride

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3718675A (en) 1970-06-18 1973-02-27 Stevens & Co Inc J P Carbonic carboxylic anhydrides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Hwa et al, Acrylic Anhydrides and Polymers Derived Therefrom, Journal of Polymer Science: Part A, vol. 2 p. 2386 (1961). *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007101563A3 (de) * 2006-03-03 2007-10-25 Cognis Ip Man Gmbh Bei raumtemperatur flüssige verbindungen
US20100204074A1 (en) * 2006-03-03 2010-08-12 Cognis Ip Management Gmbh Compounds That Are Liquid At Ambient Temperature

Also Published As

Publication number Publication date
WO1999038837A1 (fr) 1999-08-05
FR2774375A1 (fr) 1999-08-06
CZ296363B6 (cs) 2006-02-15
CN1135219C (zh) 2004-01-21
KR100401241B1 (cs) 2003-10-17
FR2774375B1 (fr) 2000-03-24
EP1071650A1 (fr) 2001-01-31
AU2167799A (en) 1999-08-16
CA2319673C (fr) 2005-03-22
JP3533178B2 (ja) 2004-05-31
CA2319673A1 (fr) 1999-08-05
KR20010040542A (ko) 2001-05-15
ID26417A (id) 2000-12-21
CZ20002145A3 (cs) 2000-09-13
CN1289320A (zh) 2001-03-28
JP2002501940A (ja) 2002-01-22

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